Process for producing crystalline poly-α-olefins with a monocyclopentadienyl transition metal catalyst system

ABSTRACT

The invention is a catalytic process using a Group IV B transition metal component and an alumoxane component to polymerize α-olefins to produce high crystallinity and high molecular weight poly-α-olefins.

This application is a continuation-in-part of U.S. patent applicationSer. No. 533,245 filed June 4, 1990 which in turn is acontinuation-in-part of U.S. patent application Ser. No. 406,945 filedSept. 13, 1989 and now abandoned.

FIELD OF THE INVENTION

This invention relates to a process for polymerizing α-olefins whichutilize certain monocyclopentadienyl metal compounds of a Group IV Btransition metal of the Periodic Table of Elements in an alumoxaneactivated catalyst system to produce crystalline poly-α-olefins,particularly polypropylene and α-olefin copolymers of propylene.

BACKGROUND OF THE INVENTION

As is well known, various processes and catalysts exist for thehomopolymerization or copolymerization of olefins. For many applicationsit is of primary importance for a polyolefin to have a high weightaverage molecular weight while having a relatively narrow molecularweight distribution. A high weight average molecular weight, whenaccompanied by a narrow molecular weight distribution, provides apolyolefin with high strength properties.

Traditional Ziegler-Natta catalysts systems--a transition metal compoundcocatalyzed by an aluminum alkyl--are capable of producing polyolefinshaving a high molecular weight but a broad molecular weightdistribution.

More recently a catalyst system has been developed wherein thetransition metal compound has two or more cyclopentadienyl ringligands--such transition metal compound being referred to herein as a"metallocene --which catalyzes the production of olefin monomers topolyolefins. Accordingly, titanocenes and zirconocenes, have beenutilized as the transition metal component in such "metallocene"containing catalyst system for the production of polyolefins andethylene-α-olefin copolymers. When such metallocenes are cocatalyzedwith aluminum alkyl--as is the case with a traditional typeZiegler-Natta catalyst system--the catalytic activity of suchmetallocene catalyst system is generally too low to be of any commercialinterest.

It has since become known that such metallocenes may be cocatalyzed withan alumoxane--rather than an aluminum alkyl--to provide a metallocenecatalyst system of high activity for the production of polyolefins.

The zirconocenes, as cocatalyzed or activated with an alumoxane, arecommonly more active than their hafnium or titanium analogous for thepolymerization of ethylene alone or together with an α-olefin comonomer.When employed in a non-supported form--i.e., as a homogeneous or solublecatalyst system--to obtain a satisfactory rate of productivity even withthe most active zirconocene species typically requires the use of aquantity of alumoxane activator sufficient to provide an aluminum atomto transition metal atom ratio (Al:TM) of at least greater than 1000:1;often greater than 5000:1, and frequently on the order of 10,000:1. Suchquantities of alumoxane impart to a polymer produced with such catalystsystem an undesirable content of catalyst metal residue, i.e., anundesirable "ash" content (the nonvolatile metal content). In highpressure polymerization procedures using soluble catalyst systemswherein the reactor pressure exceeds about 500 bar only the zirconium orhafnium species of metallocenes may be used. Titanium species ofmetallocenes are generally unstable at such high pressures unlessdeposited upon a catalyst support. A wide variety of Group IV Btransition metal compounds have been named as possible candidates for analumoxane cocatalyzed catalyst system. Although bis(cyclopentadienyl)Group IV B transition metal compounds have been the most preferred andheavily investigated for use in alumoxane activated catalyst systems forpolyolefin production, suggestions have appeared that mono andtris(cyclopentadienyl) transition metal compounds may also be useful.See, for example U.S. Pat. Nos. 4,522,982; 4,530,914 and 4,701,431. Suchmono(cyclopentadienyl) transition metal compounds as have heretoforebeen suggested as candidates for an alumoxane activated catalyst systemare mono(cyclopentadienyl) transition metal trihalides and trialkyls.

More recently, International Publication No. WO 87/03887 describes theuse of a composition comprising a transition metal coordinated to atleast one cyclopentadienyl and at least one heteroatom ligand as atransition metal component for use in an alumoxane activated catalystsystem for α-olefin polymerization. The composition is broadly definedas a transition metal, preferably of Group IV B of the Periodic Table,which is coordinated with at least one cyclopentadienyl ligand and oneto three heteroatom ligands, the balance of the transition metalcoordination requirement being satisfied with cyclopentadienyl orhydrocarbyl ligands. Catalyst systems described by this reference areillustrated solely with reference to transition metal compounds whichare metallocenes, i.e., bis(cyclopentadienyl) Group IV B transitionmetal compounds.

Even more recently, at the Third Chemical Congress of North Americanheld in Toronto, Canada in June 1988, John Bercaw reported upon effortsto use a compound of a Group III B transition metal coordinated to asingle cyclopentadienyl heteroatom bridged ligand as a catalyst systemfor the polymerization of olefins. Although some catalytic activity wasobserved under the conditions employed, the degree of activity and theproperties observed in the resulting polymer product were discouragingof a belief that such monocyclopentadienyl transition metal compoundcould be usefully employed for commercial polymerization processes.

A need still exists for discovering catalyst systems that permit theproduction of higher molecular weight polyolefins and desirably with anarrow molecular weight distribution. It is further desirable that acatalyst be discovered which will catalyze the polymerization of anα-olefin monomer(s) to a highly crystalline form of poly-α-olefin i.e.,the product polymer resin is free or substantially free of atacticstereochemical forms of poly-α-olefin molecules which are amorphous.

Polymers comprised of α-olefin monomers have hydocarbyl groups pendantfrom the polymer backbone chain. Relative to the polymer backbone chain,the pendant hydrocarbyl groups may be arranged in differentstereochemical configurations which are denominated as, for example,atactic, isotactic, or syndiotactic pendant group configuration.

The degree and type of tacticity of a polyolefin molecule is a criticaldeterminant of the physical properties which a resin composed of suchpolymer molecules will exhibit. Other critical determinants of theproperties which a resin will exhibit are the type and relativeconcentration of monomers and comonomers, the weight average molecularweight (M_(w)) of the polymer molecules comprising the resin bulk, themolecular weight distribution (MWD) and the composition distribution ofthe resin.

Important from a commercial standpoint is the rate or productivity atwhich a catalyst system will produce a poly-α-olefin resin of a desiredset of properties in terms of tacticity, weight average molecular weightand molecular weight distribution.

The weight average molecular weight (M_(w)) of a poly-α-olefin is animportant physical property determinant of the practical uses to whichsuch polymer can be put. For end use applications which require highstrength and low creep, the M_(w) of such a resin must generally be inexcess of 100,000. Further, for such high strength applications, thepoly-α-olefin resin must generally have a high degree of crystallinity.The degree of crystallinity which a poly-α-olefin is capable ofobtaining is, in major part, determined by the stereochemical regularityof the hydrocarbyl groups which are pendent to the polymer moleculebackbone, i.e., the tacticity of the polymer.

Five types of tacticity have been described in poly-α-olefins: atactic,normal isotactic, isotactic stereoblock, syndiotactic, andhemiisotactic. Although all of these tacticity configurations have beenprimarily demonstrated in the case of polypropylene, in theory each isequally possible for polymers comprised of any α-olefin, cyclic olefinor internal olefin.

Atactic poly-α-olefins are those wherein the hydrocarbyl groups pendentto the polymer molecule backbone assume no regular order in space withreference to the backbone. This random, or atactic, structure isrepresented by a polymer backbone of alternating methylene and methinecarbons, with randomly oriented branches substituting the methinecarbons. The methine carbons randomly have R and S configurations,creating adjacent pairs either of like configuration (a "meso" or "m"dyad) or of unlike configuration (a "racemic" or "r" dyad). The atacticform of a polymer contains approximately equal fractions of meso andracemic dyads.

Atactic poly-α-olefins, particularly atactic polypropylene, are solublein aliphatic and aromatic solvents at ambient temperature. Since atacticpolymers exhibit no regular order or repeating unit configurations inthe polymer chain, such atactic polymers are amorphous materials. Sinceatactic poly-α-olefins are amorphous, the resins composed thereof haveno measurable melting point. Atactic polymers exhibit little if anycrystallinity, hence they are generally unsuitable for high strengthapplications regardless of the weight average molecular weight of theresin.

Isotactic poly-α-olefins are those wherein the pendent hydrocarbylgroups are ordered in space to the same side or plane of the polymerbackbone chain. Using isotactic polypropylene as an example, theisotactic structure is typically described as having the pendent methylgroups attached to the ternary carbon atoms of successive monomericunits on the same side of a hypothetical plane through the carbonbackbone chain of the polymer, e.g., the methyl groups are all above orbelow the plane as shown below. ##STR1## The degree of isotacticregularity may be measured by NMR techniques. Bovey's NMR nomenclaturefor an isotactic pentad is . . . mmmm . . . with each "m" representing a"meso" dyad or successive methyl groups on the same side in the plane.

In the normal isotactic structure of a poly-α-olefin, all of the monomerunits have the same stereochemical configuration, with the exception ofrandom errors which appear along the polymer. Such random errors almostalways appear as isolated inversions of configuration which arecorrected in the very next α-olefin monomer insertion to restore theoriginal R or S configuration of the propagating polymer chain. Singleinsertions of inverted configuration give rise to rr triads, whichdistinguish this isotactic structure in its NMR from the isotacticstereoblock form. ##STR2## As is known in the art, any deviation orinversion in the regularity of the structure of the chains lowers thedegree of isotacticity and hence the crystallinity of which the polymeris capable. There are two other types of "errors" which have beenobserved in isotactic polymers prepared using metallocene-alumoxanecatalyst systems which act to lower the melting point and/or T_(g) ofthe material. These errors, as shown below arise when a monomer is addedto the growing polymer chain in a 1, 3 or 2,1 fashion. ##STR3##

Long before anyone had discovered a catalyst system which produced theisotactic stereoblock form of a poly-α-olefin, the possible existence ofa polymer of such micro-structure had been recognized and mechanisms forits formation had been proposed based on conventional Ziegler-Nattamechanisms in Langer, A. W., Lect. Bienn. Polym. Symp. 7th (1974); Ann.N.Y. Acad. Sci. 295, 110-126 (1977). The first example of this form ofpolypropylene and a catalyst which produces it in a pure form werereported in U.S. Pat. No. 4,522,982. The formation of stereoblockisotactic polymer differs from the formation of the normal isotacticstructure in the way that the propagation site reacts to astereochemical error in the chain. As mentioned above, the normalisotactic chain will return to the original configuration following anerror because the stereochemical regulator, the catalytic active metalspecies and its surrounding ligands, continue to dictate the samestereochemical preference during monomer insertion. In stereoblockpropagation, the catalytic active metal site itself changes from onewhich dictates a monomer insertion of R configuration to one whichdictates an S configuration for monomer insertion. The isotacticstereoblock form is shown below. ##STR4## This occurs either because themetal and its ligands change to the opposite stereochemicalconfiguration or because the configuration of the last added monomer,rather than the metal chirality, controls the configuration of the nextadded monomer. In Ziegler-Natta catalysts, including the abovereferenced system, the exact structure and dynamic properties of theactive site are not well understood, and it is virtually impossible todistinguish between the "site chirality exchange" and "chain endcontrol" mechanisms for the formation of isotactic stereoblockpoly-α-olefins.

Unlike normal isotactic polymers, the lengths of individual blocks ofthe same configuration in the stereoblock structure vary widely due tochanging reaction conditions. Since only the erroneous parts of thechains affect the crystallinity of the resin product, in general, normalisotactic polymers and isotactic stereoblock polymers of long blocklength (greater than 50 isotactic placements) have similar properties.

Highly isotactic poly-α-olefins are insoluble in xylene and are capableof exhibiting a high degree of crystallinity and are in partcharacterizable by their melting point temperature. Accordingly,isotactic poly-α-olefins are, depending upon their weight averagemolecular weight exceeding about 100,000, well suited to high strengthend use applications.

Syndiotactic poly-α-olefins are those wherein the hydrocarbyl groupspendent to the polymer molecular backbone alternate sequentially inorder from one side or plane to the opposite side or plane relative tothe polymer backbone, as shown below. ##STR5## In NMR nomenclature, thispentad is described as . . . rrrr . . . in which each r represents a"racemic" dyad, i.e., successive methyl groups on alternate sides of theplane. The percentage of r dyads in the chain determines the degree ofsyndiotacticity of the polymer.

Syndiotactic propagation has been studied for over 25 years; however,only a few good syndiospecific catalysts have been discovered, all ofwhich are extremely sensitive to monomer bulkiness. As a result,well-characterized syndiotactic polymers are limited only topolypropylenes. The molecular chain backbone of a syndiotactic polymercan be considered to be a copolymer of olefins with alternatingstereochemical configurations. Highly syndiotactic polymers aregenerally highly crystalline and will frequently have high meltingpoints similar to their isotactic polymorphs.

Like isotactic poly-α-olefins, syndiotactic poly-α-olefins are capableof exhibiting a high degree of crystallinity, hence are suitable forhigh strength applications provided their M_(w) exceeds about 100,000.Syndiotactic poly-β-olefins are in part characterized by theirexhibition of a melting point temperature.

For any of the above described materials the final resin properties andits suitability for particular applications depend on the type oftacticity, the melting point (stereoregularity), the average molecularweight, the molecular weight distribution, the type and level of monomerand comonomer, the sequence distribution, and the presence or absence ofhead or end group functionality. Accordingly, the catalyst system bywhich such a stereoregular poly-α-olefin resin is to be produced should,desirably, be versatile in terms of M_(w), MWD, tacticity type andlevel, and comonomer choice. Further, the catalyst system should becapable of producing these polymers with or without head and/or endgroup functionality, such as olefinic unsaturation. Still further, suchcatalyst system must be capable, as a commercially practical constraint,of producing such resins at an acceptable production rate. Mostpreferably, the catalyst system should be one which, at its productivityrate, provides a resin product which does not require a subsequenttreatment to remove catalyst residue to a level which is acceptable forthe resin in the end use application desired. Finally, an importantfeature of a commercial catalyst system is its adaptability to a varietyof processes and conditions.

Conventional titanium based Ziegler-Natta catalysts for the preparationof isotactic polymers are well known in the art. These commercialcatalysts are well suited for the production of highly crystalline, highmolecular weight materials. The systems are, however, limited in termsof molecular weight, molecular weight distribution, and tacticitycontrol. The fact that the conventional catalysts contain several typesof active sites further limits their ability to control the compositiondistribution in copolymerization.

More recently a new method of producing isotactic polymers from analumoxane cocatalyzed, or activated, metallocene which in its naturalstate has chirality centered at the transition metal of the metallocene,was reported in Ewen, J. A., J. Amer. Chem. Soc., v. 106, p. 6355 (1984)and Kaminsky, W., et al., Angew. Chem. Int. Ed. Eng.; 24, 507-8 (1985).

Catalysts that produce isotactic polyolefins are also disclosed in U.S.Pat. No. 4,794,096. This patent discloses a chiral, stereorigidmetallocene catalyst which is activated by an alumoxane cocatalyst whichis reported to polymerize olefins to isotactic polyolefin forms.Alumoxane cocatalyzed metallocene structures which have been reported topolymerize stereoregularly are the ethylene bridged bis-indenyl andbis-tetrahydroindenyl titanium and zirconium (IV) catalyst. Suchcatalyst systems were synthesized and studied in Wild et al., J.Organomet. Chem. 232, 233-47 (1982), and were later reported in Ewen andKaminsky et al., mentioned above, to polymerize β-olefinsstereoregularly. Further reported in West German Off DE 3443087A1(1986), but without giving experimental verification, is that the bridgelength of such stereorigid metallocenes can vary from a C₁ to C₄hydrocarbon and the metallocene rings can be simple or bi-cyclic butmust be asymmetric.

Metallocene-alumoxane catalyst generally require a high content ofalumoxane cocatalyst to be sufficiently productive for commercial use.Accordingly, metallocene-alumoxane produced isotactic poly-α-olefinresins generally have a higher than desired catalyst residue content.Hafnocene systems, which yield polymers of higher average M_(w) than thezirconium analogs, have very low activities even at high alumoxaneconcentrations.

Syndiotactic polyolefins were first disclosed by Natta et al. in U.S.Pat. No. 3,258,455. As reported, Natta obtained syndiotacticpolypropylene by using a catalyst prepared from titanium trichloride anddiethyl aluminum monochloride. A later patent to Natta et al., U.S. Pat.No. 3,305,538, discloses the use of vanadium triacetylacetonate orhalogenated vanadium compounds in combinations with organic aluminumcompounds for production of syndiotactic polypropylene.

More recently, a metallocene based catalyst system has been disclosedwhich is stated to be capable of production of syndiotacticpolypropylene of high stereoregularity. U.S. Pat. No. 4,892,851describes catalyst systems consisting of a bridged metallocene having atleast two differently substituted cyclopentadienyl ring ligands which,when cocatalyzed with an alumoxane, is stated to be capable ofproduction of syndiotactic polypropylene. Again, in commercialproduction to obtain a sufficient productivity level with such catalystsystem, the content of alumoxane is undesirably high and consequentlythe catalyst residue in the resin so produced is undesirably high.

In all methylalumoxane/metallocene catalyst systems the polymercharacteristics (M_(w), MWD, tacticity type, comonomer incorporation,etc.) are controlled either by modifications to the structure of themetallocene precursor or by adjustment of the process conditions(temperature, pressure, concentrations). In general, adjustment ofprocess conditions does not allow independent control of tacticitylevel, M_(w) and comonomer content. Addition of chain transfer agentssuch as hydrogen gas to the reactor gives lower molecular weightproducts without affecting tacticity, however, the resulting polymer nolonger has unsaturated end groups. End group functionalization is oftenan important feature in the application of low molecular weightpolymers. Given these limitations, one must prepare a wide variety ofdifferently substituted metallocene precursors to access the entirerange of desired materials.

In view of the difficulty and practical limitations in the synthesis ofbridged metallocene complexes necessary for the production of analumoxane activated metallocene catalyst system capable of producingcrystalline poly-α-olefins, it would be desirable to develop newcatalytic processes which produce highly crystalline forms ofpoly-α-olefins of high molecular weight and relatively narrow molecularweight distributions.

SUMMARY OF THE INVENTION

The process of this invention employs a catalyst system comprised of atransition metal component from Group IV B of the Periodic Table of theElements (CRC Handbook of Chemistry and Physics, 68th ed. 1987-1988) andan alumoxane component. The catalyst system may be employed in solution,slurry, gas or bulk phase polymerization procedure to producecrystalline poly-α-olefins of high weight average molecular weight andrelatively narrow molecular weight distribution.

The "Group IV B transition metal component" of the catalyst system isrepresented by the formula: ##STR6## wherein: M is Zr, Hf or Ti in itshighest formal oxidation state (+4, d⁰ complex);

(C₂ H_(4-x) R_(x)) is a cyclopentadienyl ring which is substituted withfrom zero to four substituent groups R, "x" is 0, 1, 2, 3, or 4 denotingthe degree of substitution, and each substituent group R is,independently, a radical selected from a group consisting of C₁ -C₂₀hydrocarbyl radicals, substituted C₁ -C₂₀ hydrocarbyl radicals whereinone or more hydrogen atoms is replaced by a halogen radical, an amidoradical, a phosphido radical, an alkoxy radical or any other radicalcontaining a Lewis acidic or basic functionality, C₁ -C₂₀hydrocarbyl-substituted metalloid radicals wherein the metalloid isselected from the Group IV A of the Periodic Table of Elements; andhalogen radicals, amido radicals, phosphido radicals, alkoxy radicals,aklylborido radicals or any other radical containing Lewis acidic orbasic functionality; or (C₅ H_(4-x) R_(x)) is a cyclopentadienyl ring inwhich at least two adjacent R-groups are joined forming a C₄ -C₂₀ ringto give a saturated or unsaturated polycyclic cyclopentadienyl ligandsuch as indenyl, tetrahydroindenyl, fluorenyl or octahydrofluorenyl;

(JR'_(z-2)) is a heteroatom ligand in which J is an element with acoordination number of three from Group V A or an element with acoordination number of two from Group VI A of the Periodic Table ofElements, preferably nitrogen, phosphorus, oxygen or sulfur, and each R'is, independently a radical selected from a group consisting of C₁ -C₂₀hydrocarbyl radicals, substituted C₁ -C₂₀ hydrocarbyl radicals Whereinone or more hydrogen atoms are replaced by a halogen radical, an amidoradical, a phosphido radical, an alkoxy radical or any other radicalcontaining a Lewis acidic or basic functionality, and "z" is thecoordination number of the element J;

each Q may be independently any univalent anionic ligand such as ahalide, hydride, or substituted or unsubstituted C₁ -C₂₀ hydrocarbyl,alkoxide, aryloxide, amide, arylamide, phosphide or arylphosphide,provided that where any Q is a hydrocarbyl such Q is different from (C₅H_(4-x) R_(x)), or both Q together may be an alkylidene or acyclometallated hydrocarbyl or any other divalent anionic chelatingligand;

T is a covalent bridging group containing a Group IV A or V A elementsuch as, but not limited to, a dialkyl, alkylaryl or diaryl silicon orgermanium radical, alkyl or aryl phosphine or amine radical, or ahydrocarbyl radical such as methylene, ethylene and the like;

L is a neutral Lewis base such as diethylether, tetraethylammoniumchloride, tetrahydrofuran, dimethylaniline, aniline, trimethylphosphine,n-butylamine, and the like; and "w" is a number from 0 to 3. L can alsobe a second transition metal compound of the same type such that the twometal centers M and M' are bridged by Q and Q', wherein M' has the samemeaning as M and Q' has the same meaning as Q. Such dimeric compoundsare represented by the formula: ##STR7##

The alumoxane component of the catalyst may be represented by theformulas: (R³ --Al--O)_(m) ; R⁴ (R⁵ --Al--O)_(m) ^(--AlR) ₆ or mixturesthereof, wherein R³ -R⁶ are, independently, a C₁ -C₅ alkyl group orhalide and "m" is an integer ranging from 1 to about 50 and preferablyis from about 13 to about 25.

Catalyst systems of the invention may be prepared by placing the "GroupIV B transition metal component" and the alumoxane component in commonsolution in a normally liquid alkane or aromatic solvent, which solventis preferably suitable for use as a polymerization diluent for theliquid phase polymerization of an α-olefin monomer.

Those species of the Group IV B transition metal component wherein themetal is titanium have been found to impart beneficial properties to acatalyst system which are unexpected in view of what is known about theproperties of bis(cyclopentadienyl) titanium compounds which arecocatalyzed by alumoxanes. Whereas titanocenes in their soluble form aregenerally unstable in the presence of aluminum alkyls, themonocyclopentadienyl titanium metal components of this invention,particularly those wherein the heteroatom is nitrogen, generally exhibitgreater stability in the presence of aluminum alkyls and higher catalystactivity rates.

Further, the titanium species of the Group IV B transition metalcomponent catalyst of this invention generally exhibit higher catalystactivities and the production of poly-α-olefins of greater molecularweight than catalyst systems prepared with the zirconium or hafniumspecies of the Group IV B transition metal component.

A typical polymerization process of the invention such as for thepolymerization or copolymerization of propylene comprises the steps ofcontacting propylene or other C₄ -C₂₀ α-olefins alone, or with otherunsaturated monomers including C₃ -C₂₀ α-olefins, C₄ -C₂₀ diolefins,and/or acetylenically unsaturated monomers either alone or incombination with other olefins and/or other unsaturated

monomers, with a catalyst comprising, in a suitable polymerizationdiluent, a Group IV B transition metal component illustrated above; anda methylalumoxane in an amount to provide a molar aluminum to transitionmetal ratio of from about 1:1 to about 20,000:1 or more; and reactingsuch monomer in the presence of such catalyst system at a temperature offrom about -100° C. to about 300° C. for a time of from about 1 secondto about 10 hours to produce a poly-α-olefin having a weight averagemolecular weight of from about 1,000 or less to about 2,000,000 or moreand a molecular weight distribution of from about 1.5 1 to about 15.0.

As discussed further hereafter, by proper selection of the type andpattern R substituents for the cyclopentadienyl ligand in relationshipto the type of R' substituent of the heteroatom ligand the transitionmetal component for the catalyst system may be tailored to function inthe catalyst system to produce highly crystalline poly-α-olefins to thetotal or substantial avoidance of the production of atacticpoly-α-olefin molecules which are amorphous.

DESCRIPTION OF THE PREFERRED EMBODIMENT Catalyst Component

The Group IV B transition metal component of the catalyst system isrepresented by the general formula: ##STR8## wherein M is Zr, Hf or Tiin its highest formal oxidation state (+4, d⁰ complex);

(C₅ H_(4-x) R_(x)) is a cyclopentadienyl ring which is substituted withfrom zero to four substituent groups R, "x" is 0, 2, 3, or 4 denotingthe degree of substitution, and each substituent group R is,independently, a radical selected from a group consisting of C₁ -C₂₀hydrocarbyl radicals, substituted C₁ -C₂₀ hydrocarbyl radicals whereinone or more hydrogen atoms is replaced by a halogen radical, an amidoradical, a phosphido radical, and alkoxy radical or any other radicalcontaining a Lewis acidic or basic functionality, C₁ -C₂₀hydrocarbyl-substituted metalloid radicals wherein the metalloid isselected from the Group IV A of the Periodic Table of Elements; andhalogen radicals, amido radicals, phosphido radicals, alkoxy radicals,alkylborido radicals or any other radical containing Lewis acidic orbasic functionality; or (C₅ H_(4-x) R_(x)) is a cyclopentadienyl ring inwhich two adjacent R-groups are joined forming C₄ -C₂₀ ring to give asaturated or unsaturated polycyclic cyclopentadienyl ligand such asindenyl, tetrahydroindenyl, fluorenyl or octahydrofluorenyl;

(JR'_(z-2)) is a heteroatom ligand in which J is an element with acoordination number of three from Group V A or an element with acoordination number of two from Group VI A of the Periodic Table ofElements, preferably nitrogen, phosphorus, oxygen or sulfur withnitrogen being preferred, and each R' is, independently a radicalselected from a group consisting of C₁ -C₂₀ hydrocarbyl radicals,substituted C₁ -C₂₀ hydrocarbyl radicals wherein one or more hydrogenatoms is replaced by a halogen radical, an amido radical, a phosphidoradical, an alkoxy radical or any other radical containing a Lewisacidic or basic functionality, and "z" is the coordination number of theelement J;

each Q is, independently, any univalent anionic ligand such as a halide,hydride, or substituted or unsubstituted C₁ -C₂₀ hydrocarbyl, alkoxide,aryloxide, amide, arylamide, phosphide or arylphosphide, provided thatwhere any Q is a hydrocarbyl such Q is different from (C₅ H_(4-x)R_(x)), or both Q together may be an alkylidene or a cyclometallatedhydrocarbyl or any other divalent anionic chelating ligand;

T is a covalent bridging group containing a Group IV A or V A elementsuch as, but not limited to, a dialkyl, alkylaryl or diaryl silicon orgermanium radical, alkyl or aryl phosphine or amine radical, or ahydrocarbyl radical such as methylene, ethylene and the like;

and L is a neutral Lewis base such as diethylether, tetrahydrofuran,dimethylaniline, aniline, trimethylphosphine, n-butylamine, and thelike; and "w" is a number from 0 to 3; L can also be a second transitionmetal compound of the same type such that the two metal centers M and M'are bridged by Q and Q', wherein M' has the same meaning as M and Q' hasthe same meaning as Q. Such compounds are represented by the formula:##STR9##

Examples of the T group which are suitable as a constituent group of theGroup IV B transition metal component of the catalyst system areidentified in column 1 of Table 1 under the heading "T".

Suitable, but not limiting, Group IV B transition metal compounds whichmay be utilized in the catalyst system of this invention include thosewherein the T group bridge is a dialkyl, diaryl or alkylaryl silane, ormethylene or ethylene. Exemplary of the more preferred species ofbridged Group IV B transition metal compounds are dimethylsilyl,methylphenylsilyl, diethylsilyl, ethylphenylsilyl, diphenylsilyl,ethylene or methylene bridged compounds. Most preferred of the bridgedspecies are dimethylsilyl, diethylsilyl and methylphenylsilyl bridgedcompounds.

Exemplary hydrocarbyl radicals for Q are methyl, ethyl, propyl, butyl,amyl, isoamyl, hexyl, isobutyl, heptyl, octyl, nonyl, decyl, cetyl,2-ethylhexyl, phenyl and the like, with methyl being preferred.Exemplary halogen atoms for Q include chlorine, bromine, fluorine andiodine, with chlorine being preferred. Exemplary alkoxides andaryloxides for Q are methoxide, phenoxide and substituted phenoxidessuch as 4-methylphenoxide. Exemplary amides of Q are dimethylamide,diethylamide, methylethylamide, di-t-butylamide, diisoproylamide and thelike. Exemplary aryl amides are diphenylamide and any other substitutedphenyl amides. Exemplary phosphides of Q are diphenylphosphide,dicyclohexylphosphide, diethylphosphide, dimethylphosphide and the like.Exemplary alkyldiene radicals for both Q together are methylidene,ethylidene and propylidene. Examples of the Q group which are suitableas a constituent group or element of the Group IV B transition metalcomponent of the catalyst system are identified in column 4 of Table 1under the heading "Q".

Suitable hydrocarbyl and substituted hydrocarbyl radicals, which may besubstituted as an R group for at least one hydrogen atom in thecyclopentadienyl ring, will contain from 1 to about 20 carbon atoms andinclude straight and branched alkyl radicals, cyclic hydrocarbonradicals, alkyl-substituted cyclic hydrocarbon radicals, aromaticradicals and alkyl-substituted aromatic radicals, amido-substitutedhydrocarbon radicals, phosphido-substituted hydrocarbon radicals,alkoxy-substituted hydrocarbon radicals, and cyclopentadienyl ringscontaining one or more fused saturated or unsaturated rings. Suitableorganometallic radicals, which may be substituted as an R group for atleast one hydrogen atom in the cyclopentadienyl ring, includetrimethylsilyl, triethylsilyl, ethyldimethylsilyl, methyldiethylsilyl,triphenylgermyl, trimethylgermyl and the like. Other suitable radicalsthat may be substituted for one or more hydrogen atom in thecyclopentadienyl ring include halogen radicals, amido radicals,phosphido radicals, alkoxy radicals, alkylborido radicals and the like.Examples of cyclopentadienyl ring groups (C₅ H_(4-x) R_(x)) which aresuitable as a constituent group of the Group IV B transition metalcomponent of the catalyst system are identified in Column 2 of Tableunder the heading (C₅ H_(4-x) R_(x)). Suitable R' radicals of theheteroatom J ligand are independently a hydrocarbyl radical selectedfrom a group consisting of 1 to about 20 carbon atoms and includestraight and branched alkyl radicals, cyclic hydrocarbon radicals,alkyl-substituted cyclic hydrocarbon radicals, aromatic radicals and thelike; substituted C₁ -C₂₀ hydrocarbyl radicals wherein one or morehydrogen atom is replaced by a halogen radical, an amido radical, aphosphido radical, an alkoxy radical and a alkylborido radical, or aradical containing a Lewis acidic or basic functionality, and the like.

53 cyclic Examples of heteroatom ligand groups (JR'_(z-2)) which aresuitable as a constituent group of the Group IV B transition metalcomponent of the catalyst system are identified in column 3 of Tableunder the heading (JR'_(z-2)).

Table 1 depicts representative constituent moieties for the "Group IV Btransition metal component", the list is for illustrative purposes onlyand should not be construed to be limiting in any way. A number of finalcomponents may be formed by permuting all possible combinations of theconstituent moieties with each other. Illustrative compounds are:dimethylsilylfluorenyl-t-butylamido zirconium dichloride,dimethylsilylfluorenyl-t-butylamido hafnium dichloride,dimethylsilylfluorenylcycohexylamido zirconium dihalide, anddimethylsilylfluorenylcyclohexylamido hafnium dichloride.

As noted, titanium species of the Group IV B transition metal compoundhave generally been found to yield catalyst systems which in comparisonto their zirconium or hafnium analogues, are of higher activity.Illustrative, but not limiting of the titanium species which may exhibitsuch superior properties are; dimethylsilylfluorenyl-t-butylamidotitanium dichloride, dimethylsilylindenylcyclohexylamido titaniumdichloride, dimethylsilyl-t-butylcyclopentadienylcyclododecylamidotitanium dichloride,dimethylsilylmethylcyclopentadienylcyclododecylamido titaniumdichloride,dimethylsilylmethylcyclopentadienyl-2,6-diisopropylphenylamido titaniumdichloride, dimethylsilylmethylcyclopentadienylcyclohexylamido titaniumdichloride, anddimethylsilylmethylcyclopentadienyl-2,5-di-t-butylphenylamido titaniumdichloride.

For illustrative purposes, the above compounds and those permuted fromTable 1 do not include the neutral Lewis base ligand (L). The conditionsunder which complexes containing neutral Lewis base ligands such asether or those which form dimeric compounds is determined by the stericbulk of the ligands about the metal center. For example, the t-butylgroup in Me₂ Si(Me₄ C₅)(N-t-Bu)ZrCl₂ has greater steric requirementsthan the phenyl group in Me₂ Si(Me₄ C₅)(NPh)ZrCl₂ •Et₂ O thereby notpermitting ether coordination in the former compound. Similarly, due tothe decreased steric bulk of the trimethylsilylcyclopentadienyl group in[Me₂ Si(Me₃ SiC₅ H₃)(N-t-Bu)ZrCl₂ ]₂ versus that of thetetramethylcyclopentadienyl group in Me₂ Si(Me₄ C₅)(N-t Bu)ZrCl₂, theformer compound is dimeric and the latter is not.

To illustrate members of the Group IV B transition metal component,select any combination of the species in Table An example of a bridgedspecies would be dimethylsilyclopentadienyl-t-butylamidodichlorozirconium.

                                      TABLE 1                                     __________________________________________________________________________     ##STR10##                                                                    T            (C.sub.5 H.sub.4-x R.sub.x)                                                                         (JR'.sub.z-2)                                                                            Q          M                    __________________________________________________________________________    dimethylsilyl                                                                              cyclopentadienyl       .sub.-t-butylamide                                                                      hydride    zirconium            diethylsilyl methylcyclopentadienyl                                                                              phenylamido                                                                              chloro     hafnium              di- -n-propylsilyl                                                                         1,2-dimethylcyclopentadienyl                                                                        p- -n-butylphenylamido                                                                   methyl     titanium             diisopropylsilyl                                                                           1,3-dimethylcyclopentadienyl                                                                        cyclohexylamido                                                                          ethyl                           di- -n-butylsilyl                                                                          indenyl               perflurophenylamido                                                                      phenyl                          di- .sub.-t-butylsilyl                                                                     1,2-diethylcyclopentadienyl                                                                          -n-butylamido                                                                           fluoro                          di- -n-hexylsilyl                                                                          tetramethylcyclopentadienyl                                                                         methylamido                                                                              bromo                           methylphenylsilyl                                                                          ethylcyclopentadienyl ethylamido iodo                            ethylmethylsilyl                                                                            -n-butylcyclopentadienyl                                                                            -n-propylamido                                                                           -n-propyl                      diphenylsilyl                                                                              cyclohexylmethylcyclopentadienyl                                                                    isopropylamido                                                                           isopropyl                       di(p- .sub.-t-butylphenethylsilyl)                                                          - -n-octylcyclopentadienyl                                                                         benzylamido                                                                              n-butyl                          -n-hexylmethylsilyl                                                                       β-phenylpropylcyclopentadienyl                                                                  .sub.-t-butylphosphido                                                                  amyl                            cyclopentamethylenesilyl                                                                   tetrahydroindenyl     ethylphosphido                                                                           isoamyl                         cyclotetramethylenesilyl                                                                   propylcyclopentadienyl                                                                              phenylphosphido                                                                          hexyl                           cyclotrimethylenesilyl                                                                      .sub.-t-butylcyclopentadienyl                                                                      cyclohexylphosphido                                                                      isobutyl                        dimethylgermanyl                                                                           benzylcyclopentadienyl                                                                              oxo        heptyl                          diethylgermanyl                                                                            diphenylmethylcyclopentadienyl                                                                      sulfido    octyl                           phenylamido  trimethylgermylcyclopentadienyl  nonyl                            .sub.-t-butylamido                                                                        trimethylstannylcyclopentadienyl decyl                           methylamido  triethylplumbylcyclopentadienyl  cetyl                            .sub.-t-butylphosphido                                                                    trifluromethylcyclopentadienyl   methoxy                         ethylphosphido                                                                             trimethylsilylcyclopentadienyl   ethoxy                          phenylphosphido                                                                            pentamethylcyclcopentadienyl (when y = 0)                                                                      propoxy                         methylene    fluorenyl                        butoxy                          dimethylmethylene                                                                          octahydrofluorenyl               phenoxy                         diethylmethylene                                                                           N,N-dimethylamidocyclopentadienyl                                                                              dimethylamido                   ethylene     dimethylphosphidocyclopentadienyl                                                                              diethylamido                    dimethylethylene                                                                           methoxycyclopentadienyl          methylethylamido                diethylethylene                                                                            dimethylboridocyclopentadienyl   di- .sub.-t-butylamido          dipropylethylene                                                                           (N,N-dimethylamidomethyl)cyclopentadienyl                                                                      diphenylamido                   propylene    tetrafluorocyclopentadienyl      diphenylphosphido               dimethylpropylene                             dicyclohexylphosphido           diethylpropylene                              dimethylphosphido               1,1-dimethyl-3,3-                             methylidene (both Q)            dimethylpropylene                                                             tetramethyldisiloxane                         ethylidene (both Q)             1,1,4,4-tetramethyl-                          propylidene (both Q)            disilylethylene                                                               __________________________________________________________________________

The Group IV B transition metal compounds can be prepared by reacting acyclopentadienyl lithium compound with a dihalo compound, whereupon alithium halide salt is liberated and a monohalo substituent iscovalently bound to the cyclopentadienyl compound. The so substitutedcyclopentadienyl reaction product is next reacted with a lithium salt ofa phosphide, oxide, sulfide or amide (for the sake of illustrativepurposes, a lithium amide) whereupon the halo element of the monohalosubstituent group of the reaction product reacts to liberate a lithiumhalide salt and the amine moiety of the lithium amide salt is covalentlybound to the substituent of the cyclopentadienyl reaction product. Theresulting amine derivative of the cyclopentadienyl product is thenreacted with an alkyl lithium reagent whereupon the labile hydrogenatoms, at the carbon atom of the cyclopentadienyl compound and at thenitrogen atom of the amine moiety covalently bound to the substituentgroup, react with the alkyl of the lithium alkyl reagent to liberate thealkane and produce a dilithium salt of the cyclopentadienyl compound.Thereafter the bridged species of the Group IV B transition metalcompound is produced by reacting the dilithium salt cyclopentadienylcompound with a Group IV B transition metal preferably a Group IV Btransition metal halide.

The class of transition metal components most preferred for use in theprocess for production of crystalline poly-β-olefins is that wherein thecovalent bridging group T contains silicon and the heteroatom J of theheteroatom ligand is nitrogen. Accordingly, the preferred class oftransition metal components are of the formula: ##STR11## wherein Q, L,R', R, "x" and "w" are as previously defined and R¹ and R² are eachindependently a C₁ to C₂₀ hydrocarbyl radicals, substituted C₁ to C₂₀hydrocarbyl radicals wherein one or more hydrogen atom is replaced by ahalogen atom; R¹ and R² may also be joined forming a C₃ to C₂₀ ringwhich incorporates the silicon bridge.

The alumoxane component of the catalyst system is an oligomeric compoundwhich may be represented by the general formula (R³ --Al--O)_(m) whichis a cyclic compound, or may be R⁴ (R⁵ --Al--O)_(m) -AlR⁶ ₂ which is alinear compound. An alumoxane is generally a mixture of both the linearand cyclic compounds. In the general alumoxane formula R³, R⁴, R⁵ and R⁶are, independently a C₁ -C₅ alkyl radical, for example, methyl, ethyl,propyl, butyl or pentyl and "m" is an integer from 1 to about 50. Mostpreferably, R³, R⁴, R⁵ and R⁶ are each methyl and "m" is at least 4.When an alkyl aluminum halide is employed in the preparation of thealumoxane, one or more R³⁻⁶ groups may be halide.

As is now well known, alumoxanes can be prepared by various procedures.For example, a trialkyl aluminum may be reacted with water, in the formof a moist inert organic solvent; or the trialkyl aluminum may becontacted with a hydrated salt, such as hydrated copper sulfatesuspended in an inert organic solvent, to yield an alumoxane. Generally,however prepared, the reaction of a trialkyl aluminum with a limitedamount of water yields a mixture of both linear and cyclic species ofalumoxane.

Suitable alumoxanes which may be utilized in the catalyst systems ofthis invention are those prepared by the hydrolysis of atrialkylaluminum; such as trimethylaluminum, triethyaluminum,tripropylaluminum; triisobutylaluminum, dimethylaluminumchloride,diisobutylaluminumchloride, diethylaluminumchloride, and the like. Themost preferred alumoxane for use is methylalumoxane (MAO).Methylalumoxanes having an average degree of oligomerization of fromabout 4 to about 25 ("m"=4 to 25), with a range of 13 to 25, are themost preferred.

Catalyst Systems

The catalyst systems employed in the method of the invention comprise acomplex formed upon admixture of the Group IV B transition metalcomponent with an alumoxane component. The catalyst system may beprepared by addition of the requisite Group IV B transition metal andalumoxane components to an inert solvent in which olefin polymerizationcan be carried out by a solution, slurry, gas or bulk phasepolymerization procedure.

The catalyst system may be conveniently prepared by placing the selectedGroup IV B transition metal component and the selected alumoxanecomponent, in any order of addition, in an alkane or aromatichydrocarbon solvent--preferably one which is also suitable for serviceas a polymerization diluent. When the hydrocarbon solvent utilized isalso suitable for use as a polymerization diluent, the catalyst systemmay be prepared in situ in the polymerization reactor. Alternatively,the catalyst system may be separately prepared, in concentrated form,and added to the polymerization diluent in a reactor. If desired, thecomponents of the catalyst system may be prepared as separate solutionsand added to the polymerization diluent in a reactor, in appropriateratios, as is suitable for a continuous liquid phase polymerizationreaction procedure. Alkane and aromatic hydrocarbons suitable assolvents for formation of the catalyst system and also as apolymerization diluent are exemplified by, but are not necessarilylimited to, straight and branched chain hydrocarbons such as isobutane,butane, pentane, hexane, heptane, octane and the like, cyclic andalicyclic hydrocarbons such as cyclohexane, cycloheptane,methylcyclohexane, methylcycloheptane and the like, and aromatic andalkyl-substituted aromatic compounds such as benzene, toluene, xyleneand the like. Suitable solvents also include liquid olefins which mayact as monomers or comonomers including ethylene, propylene, 1-butene,1-hexene and the like.

In accordance with this invention optimum results are generally obtainedwherein the Group IV B transition metal compound is present in thepolymerization diluent in a concentration of from about 0.0001 to about1.0 millimoles/liter of diluent and the alumoxane component is presentin an amount to provide a molar aluminum to transition metal ratio offrom about to about 20,000:1. Sufficient solvent should be employed soas to provide adequate heat transfer away from the catalyst componentsduring reaction and to permit good mixing.

The catalyst system ingredients--that is, the Group IV B transitionmetal, the alumoxane, and polymerization diluent--can be added to thereaction vessel rapidly or slowly. The temperature maintained during thecontact of the catalyst components can vary widely, such as, forexample, from -10° to 300° C. Greater or lesser temperatures can also beemployed. Preferably, during formation of the catalyst system, thereaction is maintained within a temperature of from about 25° to 100°C., most preferably about 25° C.

At all times, the individual catalyst system components, as well as thecatalyst system once formed, are protected from oxygen and moisture.Therefore, the reactions to prepare the catalyst system are performed inan oxygen and moisture free atmosphere and, where the catalyst system isrecovered separately it is recovered in an oxygen and moisture freeatmosphere. Preferably, therefore, the reactions are performed in thepresence of an inert dry gas such as, for example, helium or nitrogen.

Polymerization Process

In a preferred embodiment of the process of this invention, the catalystsystem is utilized in the liquid phase (slurry, solution, suspension orbulk phase or combination thereof), high pressure fluid phase or gasphase polymerization of an α-olefin monomer. These processes may beemployed singularly or in series. The liquid phase process comprises thesteps of contacting an α-olefin monomer with the catalyst system in asuitable polymerization diluent and reacting said monomer in thepresence of said catalyst system for a time and at a temperaturesufficient to produce a poly-α-olefin of high crystallinity andmolecular weight.

The monomer for such process comprises an α-olefin having 3 to 20 carbonatoms. Propylene is a preferred monomer. Homopolymers of higher α-olefinsuch as butene, styrene and copolymers thereof with ethylene and/or C₄or higher α-olefins, diolefins, cyclic olefins and internal olefins canalso be prepared. Conditions most preferred for the homo- orcopolymerization of the α-olefin are those wherein an α-olefin issubmitted to the reaction zone at pressures of from about 0.09 psia toabout 50,000 psia and the reaction temperature is maintained at fromabout -100° to about 300° C. The aluminum to transition metal molarratio is preferably from about 1:1 to 18,000 to 1. A more preferablerange would be 1:1 to 2000:1. The reaction time is preferably from about10 seconds to about 1 hour. Without limiting in any way the scope of theinvention, one means for carrying out the process of the presentinvention for production of a polymer is as follows: in a stirred-tankreactor liquid α-olefin monomer is introduced, such as propylene. Thecatalyst system is introduced via nozzles in either the vapor or liquidphase. The reactor contains a liquid phase composed substantially of theliquid α-olefin monomer together with a vapor phase containing vapors ofthe monomer. The reactor temperature and pressure may be controlled viareflux of vaporizing α-olefin monomer (autorefrigeration), as well as bycooling coils, jackets etc. The polymerization rate is controlled by theconcentration of catalyst.

By appropriate selection of (1) Group IV B transition metal componentfor use in the catalyst system; (2) the type and amount of alumoxaneused; (3) the polymerization diluent type and volume; (4) reactiontemperature; and (5) reaction pressure, one may tailor the productpolymer to the weight average molecular weight value desired while stillmaintaining the molecular weight distribution to a value below about4.0.

The preferred polymerization diluents for practice of the process of theinvention are aromatic diluents, such as toluene, or alkanes, such ashexane.

The resins that are prepared in accordance with this invention can beused to make a variety of products including films and fibers.

EXAMPLES

In the examples which illustrate the practice of the invention theanalytical techniques described below were employed for the analysis ofthe resulting polyolefin products. Molecular weight determinations forpolyolefin products were made by Gel Permeation Chromatography (GPC)according to the following technique. Molecular weights and molecularweight distributions were measured using a Waters 150 gel permeationchromatograph equipped with a differential refractive index (DRI)detector and a Chromatix KMX-6 on-line light scattering photometer. Thesystem was used at 135° C. with 1,2,4-trichlorobenzene as the mobilephase. Shodex (Showa Denko America, Inc.) polystyrene gel columns 802,803, 804 and 805 were used. This technique is discussed in "LiquidChromatography of Polymers and Related Materials III", J. Cazes editor,Marcel Dekker. 1981, p. 207, which is incorporated herein by reference.No corrections for column spreading were employed; however, data ongenerally accepted standards, e.g. National Bureau of StandardsPolyethylene 1484 and anionically produced hydrogenated polyisoprenes(an alternating ethylene-propylene copolymer) demonstrated that suchcorrections on M_(w) /Mn (=MWD) were less than 0.05 units. M_(w) /Mn wascalculated from elution times. The numerical analyses were performedusing the commercially available Beckman/CIS customized LALLS softwarein conjunction with the standard Gel Permeation package, run on a HP1000 computer.

Calculations involved in the characterization of polymers by ¹³ CNMRfollow the work of F. A. Bovey in "Polymer Conformation andConfiguration" Academic Press, New York, 1969.

The following examples are intended to illustrate specific embodimentsof the invention and are not intended to limit the scope of theinvention.

All procedures were performed under an inert atmosphere of helium ornitrogen. Solvent choices are often optional, for example, in most caseseither pentane or 30-60 petroleum ether can be interchanged. Thelithiated amides were prepared from the corresponding amines and eithern-BuLi or MeLi. Published methods for preparing LiHC₅ Me₄ include C. M.Fendrick et al. Organometallics, 3, 819 (1984) and F. H. Kohler and K.H. Doll, Z. Naturforsch, 376, 144 (1982). Lithiated substitutedcyclopentadienyl compounds are typically prepared from the correspondingcyclopentadienyl ligand and D-BuLi or MeLi, or by reaction of MeLi withthe proper fulvene. TiCl₄, ZrCl₄ and HfCl₄ were purchased from eitherAldrich Chemical Company or Cerac. TiCl₄ was typically used in itsetherate form. The etherate, TiCl₄ •2Et₂ O, can be prepared by gingerlyadding TiCl₄ to diethylether. Amines, silanes and lithium reagents werepurchased from Aldrich Chemical Company or Petrarch Systems.Methylalumoxane was supplied by either Schering or Ethyl Corp.

Examples of Group IV B Transition Metal--Components Example A

Compound A: Part 1. Me₂ SiCl₂ (7.5 ml, 0.062 mol) was diluted with ˜30ml of THF. A t-BuH₄ C₅ Li solution (7.29 g, 0.057 mol, ˜100 ml of THF)was slowly added, and the resulting mixture was allowed to stirovernight. The THF was removed in vacuo. Pentane was added toprecipitate the LiCl, and the mixture was filtered through Celite. Thepentane was removed from the filtrate leaving behind a pale yellowliquid, Me₂ Si(t-BuC₅ H₄)Cl (10.4 g, 0.048 mol).

Part 2. Me₂ Si(t-BuC₅ H₄)Cl (8.0 g, 0.037 mol) was diluted with thf. Tothis, LiHNChd 12H₂₃ (7.0 g, 0.037 mol) was slowly added. The mixture wasallowed to stir overnight. The solvent was removed via vacuum andtoluene was added to precipitate the LiCl. The toluene was removed fromthe filtrate leaving behind a pale yellow liquid, Me₂ Si(t-BuC₅H₄)(HNC₁₂ H₂₃)(12.7 g, 0.035 mol).

Part 3. Me₂ Si(t-BuC₅ H₄)(HNC₁₂ H₂₃)(12.7 g, 0.035 mol) was diluted withether. To this, MeLi (1.4M in ether, 50 ml, 0.070 mol) was slowly added.This was allowed to stir for two hours prior to removing the solvent viavacuum. The product, Li₂ [Me₂ Si(t-BuC₅ H₃)(NC₁₂ H₂₃)] (11.1 g, 0.030mol) was isolated.

Part 4. Li₂ [Me₂ Si(t-BuC₅ H₃)(NC₁₂ H₂₃)] (10.9 g,0.029 mol) wassuspended in cold ether. TiCl₄ •2Et₂ O (9.9 g, 0.029 mol) was slowlyadded and the mixture was allowed to stir overnight. The solvent wasremoved via vacuum. Dichloromethane was added and the mixture wasfiltered through Celite. The solvent was removed and pentane was added.The product is completely soluble in pentane. This solution was passedthrough a column containing a top layer of silica and a bottom layer ofCelite. The filtrate was then evaporated down to an olive green coloredsolid identified as Me₂ Si(t-BuC₅ H₃)(NC₁₂ H₂₃)TiCl₂ (5.27 g, 0.011mol).

Example B

Compound B: Part 1. Me₂ SiCl₂ (210 ml, 1.25 mol) was diluted with amixture of ether and THF. LiMeC₅ H₄ (25 g, 0.29 mol) was slowly added,and the resulting mixture was allowed to stir for a few hours, afterwhich time the solvent was removed in vacuo. Pentane was added toprecipitate the LiCl, and the mixture was filtered through Celite. Thepentane was removed from the filtrate leaving behind a pale yellowliquid, Me₂ Si(MeC₅ H₄)Cl.

Part 2. Me₂ Si(MeC₅ H₄)Cl (10.0 g, 0.058 mol) was diluted with a mixtureof ether and THF. To this, LiHNC₁₂ H₂₃ (11.0 g, 0.058 mol) Was slowlyadded. The mixture was allowed to stir overnight. The solvent wasremoved via vacuum and toluene and pentane were added to precipitate theLiCl. The solvent was removed from the filtrate leaving behind a paleyellow liquid, Me₂ Si(MeC₅ H₄)(HNC₁₂ H₂₃) (18.4 g, 0.058 mol).

Part 3. Me₂ Si(MeC₅ H₄)(HNC₁₂ H₂₃) (18.4 g, 0.058 mol) was diluted inether. MeLi (1.4M in ether, 82 ml, 0.115 mol) was slowly added. Thereaction was stirred for several hours before reducing the volume andthen filtering off the white solid, Li₂ [Me₂ Si(MeC₅ H₃)(NC₁₂ H₂₃)](14.2 g, 0.043 mol).

Part 4. Li₂ [Me₂ Si(MeC₅ H₃)(NC₁₂ H₂₃)](7.7 g,0.023 mol) was suspendedin cold ether. TiCl₄ •2Et₂ O (7.8 g, 0.023 mol) was slowly added and themixture was allowed to stir overnight. The solvent was removed viavacuum. Dichloromethane was added and the mixture was allowed to stirovernight. The solvent was removed via vacuum. Dichloromethane was addedand the mixture was filtered through Celite. The dichloromethane wasreduced in volume and petroleum ether was added to maximizeprecipitation. This mixture was then refrigerated for a short period oftime prior to filtering off a yellow/green solid identified as Me₂(Si(MeC₅ H₃)(NC₁₂ H₂₃)TiCl₂ (5.87 g, 0.013 mol).

Example C

Compound C: Part 1. Me₂ SiCl₂ (150 ml, 1.24 mol) was diluted with ˜200ml of ether. Li(C₁₃ H₉) •Et₂ O (lithiated fluorene etherate, 28.2 g,0.11 mol) was slowly added. The reaction was allowed to stir for -1 hrprior to removing the solvent via vacuum. Toluene was added and themixture was filtered through Celite to remove the LiCl. The solvent wasremoved from the filtrate, leaving behind the off-white solid, Me₂Si(C₁₃ H₉)Cl (25.4 g, 0.096 mol).

Part 2. Me₂ Si(C₁₃ H₉)Cl (8.0 g, 0.031 mol) was suspended in ether andTHF in a ratio of 5:1. LiHNC₆ H₁₁ (3.25 g, 0.031 mol) was slowly added.The reaction mixture was allowed to stir overnight. After removal of thesolvent via vacuum, toluene was added and the mixture was filteredthrough Celite to remove the LiCl. The filtrate was reduced in volume togive a viscous orange liquid. To this liquid which was diluted in ether,43 ml of 1.4M MeLi (0.060 mol) was added slowly. The mixture was allowedto stir overnight. The solvent was removed via vacuum to produce 13.0 g(0.031 mol) of Li₂ [Me₂ Si(C₁₃ H₈)(NC₆ H₁₁)]•1.25 Et₂ O.

Part 3. Li₂ [Me₂ Si(C₁₃ H₈)(NC₆ H₁₁)]•1.25Et₂ O (6.5 g, 0.15 mol) wasdissolved in cold ether. TiCl₄ •2Et₂ O (5.16 g, 0.017 mol) was slowlyadded. The mixture was allowed to stir overnight. The solvent wasremoved via vacuum and methylene chloride was added. The mixture wasfiltered through Celite to remove the LiCl. The filtrate was reduced involume and petroleum ether was added. This was refrigerated to maximizeprecipitation prior to filtering off the solid. Since the solidcollected was not completely soluble in toluene, it was mixed withtoluene and filtered to remove the toluene insolubles. The filtrate wasreduced in volume and petroleum ether was added to induce precipitation.The mixture was refrigerated prior to filtration. The red-brown solidMe₂ Si(C₁₃ H₈)(NC₆ H₁₁)TiCl₂ was isolated (2.3 g, 5.2 mmol).

Example D

Compound D: Part 1. Me₂ Si(C₁₃ H₉)Cl was prepared as described inExample C for the preparation of compound C, Part 1.

Part 2. Me₂ Si(C₁₃ H₉)Cl (8.0 g, 0.031 mol) was diluted in ether.LiHN-t-Bu (2.4 g, 0.030 mol) was slowly added and the mixture wasallowed to stir overnight. The solvent was removed in vacuo andmethylene chloride was added to precipitate out the LiCl which wasfiltered off. The solvent was removed from the filtrate leaving behindan oily yellow liquid identified as Me₂ Si(C₁₃ H₉)(NH-t-Bu) (8.8 g,0.028 mol).

Part 3. Me₂ Si(C₁₃ H₉)(NH-t-Bu) (8.8 g, 0.028 mol) was diluted withether. MeLi (1.4 M, 41 ml, 0.057 mol) was slowly added and the reactionwas allowed to stir for about two hours. The solvent was removed viavacuum leaving behind an orange solid identified as Li₂ [Me₂ Si(C₁₃H₈)(N-t-Bu)]•Et₂ O.

Part 4. Li₂ [Me₂ Si(C₁₃ H₈)(N-t-Bu)]•Et₂ O (3.0 g, 0.008 mol) wasdissolved in ether. ZrCl₄ (1.84 g, 0.008 mol) was slowly added and themixture was allowed to stir overnight. The solvent was removed viavacuum and a mixture of toluene and methylene chloride was added toprecipitate the LiCl which was filtered off. The solvent was reduced involume and petroleum ether was added to precipitate the product. Themixture was refrigerated to maximize precipitation prior to beingfiltered. Me₂ Si(C₁₃ H₈)(N-t-Bu)ZrCl₂ was isolated as a yellow solid(1.9 g, 0.005 mol.)

Example E

Compound E: Part 1. Li₂ [Me₂ Si(C₁₃ H₈)(NC₆ H₁₁)•1.25 Et₂ O was preparedas described in Example C, Part 3 for the preparation of Compound C.

Part 2. Li₂ [Me₂ Si(C₁₃ H₈)(NC₆ H₁₁)•1.25Et₂ O (3.25 g, 7.6 mmol) wasdissolved in ether. HfCl₄ (1.78, 5.6 mmol) was slowly added. The orangemixture was allowed to stir overnight. The solvent was removed viavacuum and a mixture of toluene and methylene chloride was added. Themixture was filtered through Celite to remove LiCl. The filtrate wasreduced in volume and petroleum ether was added. This was refrigeratedto maximize precipitation prior to filtering off the orange solid. Afterfiltration of the mixture, the product Me₂ Si(C₁₃ H₈)(NC₆ H₁₁)HfCl₂ (1.9g, 3.3 mmol) was isolated.

Example F

Compound F: Part 1. Li₂ [Me₂ Si(C₁₃ H₈)(N-t-Bu)]•Et₂ O was prepared asdescribed in Example D, Part 3 for the preparation of Compound D.

Part 2. Li₂ [Me₂ Si(C₁₃ H₈)(N-t-Bu)]•Et₂ O (2.8 g, 7.3 mmol wasdissolved in ether. HfCl₄ (2.35 g, 7.3 mmol) was slowly added and thereaction mixture was allowed to stir over night. The solvent was removedvia vacuum and toluene was added. The mixture was filtered throughCelite to remove LiCl. The filtrate was reduced in volume and petroleumether was added. This was refrigerated to maximize precipitation priorto filtering off the pale orange solid. After filtration of the mixture,the product Me₂ Si(C₁₃ H₈)(N-t-Bu)HfCl₂ (1.9 g, 3.5 mmol) was isolated.

Example G

Compound G: Part 1. LiC₉ H₇ (40 g, 0.33 mol, lithiated indene=Li(Hind))was slowly added to Me₂ SiCl₂ (60 ml, 0.49 mol) in ether and THF. Thereaction was allowed to stir for 1.5 hours prior to removing the solventvia vacuum. Petroleum ether was then added, and the LiCl was filteredoff. The solvent was removed from the filtrate via vacuum, leavingbehind the pale yellow liquid, (Hind)Me₂ SiCl (55.7 g, 0.27 mol).

part 2. (Hind)Me₂ SiCl (17.8 g, 0.085 mol) was diluted with ether.LiHNC₆ H₁₁ (9.0 g, 0.086 mol) was slowly added and the mixture wasallowed to stir overnight. The solvent was removed via vacuum andpetroleum ether was added. The LiCl was filtered off and the solvent wasremoved via vacuum to give a viscous yellow liquid. To this liquid whichwas diluted in ether, 118 ml of 1.4 M MeLi (0.17 mol) was added and themixture was allowed to stir for two hours. The solvent was removed viavacuum yielding the pale yellow solid, Li₂ [Me₂ Si(ind)(NC₆ H₁₁)]•1/2Et₂O (27.3 g. 0.085 mol).

Part 3. Li₂ [Me₂ Si(ind)(NC₆ H₁₁)]•1/2Et₂ O (10.0 g, 0.031 mol) wassuspended in ether. A small amount of TiCl₄ •2Et₂ O was added and themixture was stirred for approximately five minutes. The mixture was thencooled to -30° C. before adding the remaining TiCl₄ •2Et₂ O (total: 10.5g, 0.031 mol). The mixture was allowed to stir over night. The solventwas removed via vacuum and methylene chloride was added. The mixture wasfiltered through Celite and the brown filtrate was reduced in volume.Petroleum ether was added and the mixture was refrigerated to maximizeprecipitation. A brown solid was filtered off which was mixed in hottoluene and filtered through Celite to remove the toluene insolubles.Petroleum ether was added to the filtrate and the mixture was againrefrigerated prior to filtering off the solid. This solid wasrecrystallized twice; once from ether and petroleum ether and once fromtoluene and petroleum ether. The last recrystallization isolated thepale brown solid, Me₂ Si(ind)(NC.sub. 6 H₁₁)TiCl₂ (1.7 g, 4.4 mmol).

Example H

Compound H: Part 1. Me₂ Si(MeC₅ H₄)Cl was prepared as described inExample B, Part 1 for the preparation of Compound B.

Part 2. Me₂ Si(MeC₅ H₄)Cl (11.5 g, 0.067 mol) was diluted with ether.LiHN-2,6-i-PrC₆ H₃ (12.2 g, 0.067 mol) was slowly added. The mixture wasallowed to stir overnight. The solvent was removed via vacuum and amixture of toluene and dichloromethane was added to precipitate theLiCl. The mixture was filtered and the solvent was removed from thefiltrate leaving behind the viscous yellow liquid, Me₂ Si(MeC₅H₄)(HN-2,6-i-PrC₆ H₃). Assuming a ˜95% yield, 90 ml of MeLi (1.4 M inether, 0.126 mol) was slowly added to a solution of Me₂ Si(MeC₅H₄)(HN-2,6-i-PrC₆ H₃)in ether. This was allowed to stir overnight. Thesolvent was reduced in volume and the mixture was filtered and the solidcollected was washed with aliquots of ether, then vacuum dried. Theproduct, Li₂ [Me₂ Si(MeC₅ H₃)(N-2,6-i-PrC₆ H₃)], was isolated (13.0 g,0.036 mol).

Part 3. Li₂ [Me₂ Si(MeC₅ H₃)(N-2,6-i-PrC₆ H₃)] (7.0 g, 0.019 mol) wasdiluted in cold ether. TiCl₄ •2Et₂ O (6.6 g, 0.019 mol) was slowly addedand the mixture was allowed to stir overnight. The solvent was removedvia vacuum. Dichloromethane was added and the mixture was filteredthrough Celite. The dichloromethane was reduced in volume and petroleumether was added to maximize precipitation. This mixture was thenrefrigerated for a short period of time prior to filtering off an orangesolid which was recrystallized from dichloromethane and identified asMe₂ Si(MeC₅ H₃)(N-2,6-i-PrC₆ H₃)TiCl₂ (1.75 g, 4.1 mmol).

Example I

Compound I: Part 1. Me₂ Si(MeC₅ H₄)Cl was prepared as described inExample B, Part 1 for the preparation of compound B.

part 2. Me₂ Si(MeC₅ H₄)Cl (10.0 g, 0.058 mol) was diluted with ether.LiHNC₆ H₁₁ (6.1 g, 0.58 mol) was slowly added and the mixture wasallowed to stir overnight. The solvent was removed via vacuum andtoluene was added to precipitate the LiCl. The toluene was removed fromthe filtrate leaving behind a pale yellow liquid, Me₂ Si(MeC₅ H₄)(HNC₆H₁₁). The yield was assumed to be ˜95%. Based on this, two equivalentsof MeLi (1.4 M in ether, 0.11 mol, 80 ml) was slowly added to an ethersolution of Me₂ Si(MeC₅ H₄)(HNC₆ H₁₁). This was stirred for a few hoursbefore removing the solvent and isolating the product, Li₂ [Me₂ Si(MeC₅H₃)(NC₆ H₁₁)] (12.3 g, 0.050 mol).

Part 3. Li₂ [Me₂ Si(MeC₅ H₃)(NC₆ H₁₁)] (7.25 g, 0.029 mol) was suspendedin cold ether. TiCl₄.2Et₂ O (9.9 g, 0.029 mol) was slowly added and themixture was allowed to stir overnight. The solvent was removed viavacuum. Dichloromethane was added and the mixture was filtered throughCelite. The dichloromethane was reduced in volume and petroleum etherwas added to maximize precipitation. This mixture was then refrigeratedfor a short period of time prior to filtering off a maize colored solidwhich was recrystallized from dichloromethane and identified as Me₂Si(MeC₅ H₃)(NC₆ H₁₁)TiCl₂ (3.25 g, 9.2 mmol).

Example J

Compound J: Part 1. Me₂ Si(MeC₅ H₄)Cl was prepared as described inExample B, Part 1 for the preparation of Compound B.

Part 2. Me₂ Si(MeC₅ H₄)Cl (10.0 g, 0.059 mol) was diluted with ether.LiHN-2,5-t-Bu₂ C₆ H₃ (12.2 g, 0.58 mol) was slowly added and the mixturewas allowed to stir overnight. The solvent was removed via vacuum andtoluene was added to precipitate the LiCl. The toluene was removed fromthe filtrate leaving behind a pale yellow liquid, Me₂ Si(MeC₅H₄)(HN-2,5-t-Bu₂ C₆ H₃). The yield was assumed to be ˜95%. Based onthis, two equivalents of MeLi (1.4 M in ether, 0.11 mol, 80 ml) wasslowly added to an ether solution of Me₂ Si(MeC₅ H₄)(HN-2,5-t-Bu₂ C₆H₃). This was stirred for a few hours before removing the solvent andisolating the product, Li₂ [Me₂ Si(MeC₅ H₃)(N-2,5-t-Bu₂ C₆ H₃)] (7.4 g,0.021 mol).

Part 3. Li₂ [Me₂ Si(MeC₅ H₃)(N-2,5-t-Bu₂ C₆ H₃)] (6.3 g, 0.018 mol) wassuspended in cold ether. TiCl₄ •2Et₂ O (6.0 g, 0.18 mol) was slowlyadded and the mixture was allowed to stir overnight. The solvent wasremoved via vacuum. Dichloromethane was added and the mixture wasfiltered through Celite. The dichloromethane was reduced in volume andpetroleum ether was added to maximize precipitation. This mixture wasthen refrigerated for a short period of time prior to filtering off asolid which was recrystallized from dichloromethane giving an orangesolid identified as Me₂ Si(MeC₅ H₃)(N-2,5-t-Bu₂ C₆ H₃)TiCl₂ (2.4 g, 5.2mmol).

Examples 1-10 of Polymerization Example 1 Polymerization--Compound A

Using the same reactor design and general procedure already described incopending application U.S. Ser. No. 533,245 already described 400 ml oftoluene, 100 ml of propylene, 2.5 ml of 1.0M MAO, and 1.58 mg ofcompound A (1.0 ml of 15.8 mg of compound a in 10 ml of toluene) wereadded to the reactor. The reactor was heated at 30° C. and the reactionwas allowed to run for 30 minutes followed by rapidly cooling andventing the system. The polymer was precipitated out and filtered offgiving 0.7 g of crystalline polypropylene (MW=169,500, MWD=1.605,m=0.725, r=0.275, 115 chain defects/1000 monomer units).

Example 2 Polymerization--Compound B

Using the same reactor design and general procedure already described,100 ml of toluene, 100 ml of propylene, 2.5 ml of 1.0M MAO, and 0.92 mgof compound B (1.0 ml of 9.2 mg of compound B in 10 ml of toluene) wereadded to the reactor. The reactor was heated at 30° C. and the reactionwas allowed to run for 30 minutes followed by rapidly cooling andventing the system. The polymer was precipitated out and filtered offgiving 0.5 g of crystalline polypropylene (MW=279,800, MWD=1.823,m=0.547, r=0.453, 180 chain defects/1000 monomer units) in addition to0.2 g of amorphous polypropylene.

Example 3 Polymerization--Compound C

Using the same reactor design and general procedure already described,100 ml of toluene, 100 ml of propylene, 5 ml of 1.0 M MAO, and 2.46 mgof compound C (2 ml of 12.3 mg of compound C in 10 ml of toluene) wereadded to the reactor. The reactor was heated at 30° C. and the reactionwas allowed to run for 1 hour, followed by rapidly cooling and ventingthe system. The polymer was precipitated out and filtered off giving 2.2g of crystalline polypropylene (MW=29,000, MWD=2.673, m=0.356, r=0.641,110.5 chain defects/1000 monomer units, mp=143° C.) and a trace amountof amorphous polypropylene which was isolated from the filtrate.

Example 4 Polymerization--Compound D

Using the same reactor design and general procedure already described,100 ml of toluene, 200 ml of propylene, 5 ml of 1.0M MAO, and 6.4 mg ofcompound D (5 ml of 12.4 mg of compound D in 10 ml of toluene) wereadded to the reactor. The reactor was heated at 30° C. and the reactionwas allowed to run for one hour, followed by rapidly cooling and ventingthe system. The polymer was precipitated out and filtered off giving 1.4g of crystalline polypropylene (MW=76,900, MWD=1.553, m= 0.982, r=0.18,9.1 defects/1000 monomer units, mp=145° C.) and trace amounts ofamorphous polypropylene which was isolated from the filtrate.

Example 5 Polymerization--Compound E

Using the same reactor design and general procedure already described,100 ml of toluene, 200 ml of propylene, 5.0 ml of 1.0M MAO, and 8.0 mgof compound E (5.0 ml of 16.0 mg of compound E in 10 ml of toluene) wereadded to the reactor. The reactor was heated at 30° C. and the reactionwas allowed to run for 1 hour followed by rapidly cooling and ventingthe system. The polymer was precipitated out and filtered off giving 2.3g of crystalline polypropylene (MW=68,600, MWD=1.718, m=0.945, r=0.055,21.6 chain defects/1000 monomer units, mp=149° C.).

Example 6 Polymerization--Compound F

Using the same reactor design and general procedure already described,100 ml of hexane, 500 ml of propylene, 10.0 ml of 1.0M MAO, and 3.4 mgof compound F (2.0 ml of 17.0 mg of compound F in 10 ml of toluene) wereadded to the reactor. The reactor was heated at 30° C. and the reactionwas allowed to run for 2.5 hours followed by rapidly cooling and ventingthe system. The polymer was precipitated out and filtered off giving 3.1g of crystalline polypropylene (MW=70,600, MWD=1.726, m =0.858, r=0.143, 45.2 chain defects/1000 monomer units, mp=144° C.).

Example 7 Polymerization--Compound G

Using the same reactor design and general procedure already described,200 ml of toluene, 200 ml of propylene, 5.0 ml of 1.0M MAO, and 5.5 mgof compound G (5.0 ml of 11.0 mg of compound G in 10 ml of toluene) wereadded to the reactor. The reactor was heated at 30° C. and the reactionwas allowed to run for 1.0 hour followed by rapidly cooling and ventingthe system. The polymer was precipitated out and filtered off giving 2.4g of crystalline polypropylene (MW=71,300, MWD=1.812, m=0.866, r=0.134,52 chain defects/1000 monomer units, mp=147° C.) and trace amounts ofamorphous polymer.

Example 8 Polymerization--Compound H

Using the same reactor design and general procedure already described,100 ml of toluene, 100 ml of propylene, 2.5 ml of 1.0M MAO, and 0.86 mgof compound H (1.0 ml of 8.6 mg of compound H in 10 ml of toluene) wereadded to the reactor. The reactor was heated at 30° C. and the reactionwas allowed to run for one hour followed by rapidly cooling and ventingthe system. The polymer was precipitated out and filtered off giving 2.8g of crystalline polypropylene (MW=170,300, MWD=2.275, m=b 0.884,r=0.116, 46.5 chain defects/1000 monomer units, mp=151° C.).

Example 9 Polymerization--Compound I

Using the same reactor design and general procedure already described,100 ml of toluene, 100 ml of propylene, 2.5 ml of 1.0M MAO, and 0.70 mgof compound I (1.0 ml of 7.0 mg of compound I in 10 ml of toluene) wereadded to the reactor. The reactor was heated at 30° C. and the reactionwas allowed to run for one hour followed by rapidly cooling and ventingthe system. The polymer was precipitated out and filtered off giving 2.3g of crystalline polypropylene (MW=145,500, MWD=3.551, m=0.860, r=0.140,57.1 chain defects/1000 monomer units, mp=151°0 C.).

Example 10 Polymerization--Compound J

Using the same reactor design and general procedure already described,100 ml of toluene, 100 ml of propylene, 2.5 ml of 1.0M MAO, and 1.0 mgof compound J 1.0 ml of 10.0 mg of compound J in 10 ml of toluene) wereadded to the reactor. The reactor was heated at 30° C. and the reactionwas allowed to run for one hour followed by rapidly cooling and ventingthe system. The polymer was precipitated out and filtered off giving 1.4g of crystalline polypropylene (MW=211,400, MWD=2.734, m=0.750, r=0.250,97.3 chain defects/1000 monomer units, mp=144° C.).

Table 2 summarizes the polymerization conditions employed and theproperties obtained in the product polymers as set forth in Examples1-10 above.

                                      TABLE 2                                     __________________________________________________________________________                                 Ac-                                                           Methyl-         tivity                      Chain                   Transition                                                                              alum-           g poly-                     Defects/                Metal     oxane    RXN    mer/                        1000                 Exp.                                                                             Component (TMC)                                                                         MAO  MAO:                                                                              Time                                                                             Yield                                                                             mmole°                                                                             MP              Monomer              No.                                                                              Type                                                                             mmole  mmole                                                                              TMC (hr)                                                                             (g) hr  MW  MWD (°C.)                                                                     m  mmmm                                                                              r  rrrr                                                                             Units                __________________________________________________________________________    1  A  3.30 × 10.sup.-3                                                               2.5  760 0.5                                                                              0.7 424 169,500                                                                           1.605                                                                             na.sup.a                                                                         0.725                                                                            0.446                                                                             0.275                                                                            0.022                                                                            115                  2  B  2.11 × 10.sup.-3                                                               2.5  1200                                                                              0.5                                                                              0.5 474 279,800                                                                           1.823                                                                             na.sup.a                                                                         0.547                                                                            0.227                                                                             0.453                                                                            0.063                                                                            180                  3  C  5.61 × 10.sup.-3                                                               5.0  900 1.0                                                                              2.2 392 29,000                                                                            2.673                                                                             143                                                                              0.359                                                                            0.151                                                                             0.641                                                                            0.353                                                                            110.5                4  D  1.41 × 10.sup.-3                                                               5.0  360 1.0                                                                              1.4 100 76,900                                                                            1.553                                                                             145                                                                              0.982                                                                            0.934                                                                             0.018                                                                            0.000                                                                            9.1                  5  E  1.41 × 10.sup.-3                                                               5.0  360 1.0                                                                              2.3 164 68,600                                                                            1.718                                                                             149                                                                              0.945                                                                            0.883                                                                             0.055                                                                            0.007                                                                            21.6                 6  F  6.26 × 10.sup.-3                                                               10.0 1600                                                                              2.5                                                                              3.1 198 70,600                                                                            1.726                                                                             144                                                                              0.858                                                                            0.756                                                                             0.143                                                                            0.036                                                                            45.2                 7  G  1.42 × 10.sup.-3                                                               5.0  350 1.0                                                                              2.4 169 71,300                                                                            1.812                                                                             147                                                                              0.866                                                                            0.747                                                                             0.134                                                                            0.016                                                                            52                   8  H  2.00 × 10.sup.-3                                                               2.5  1250                                                                              1.0                                                                              2.8 1400                                                                              170,300                                                                           2.275                                                                             151                                                                              0.884                                                                            0.774                                                                             0.116                                                                            0.012                                                                            46.5                 9  I  1.99 × 10.sup.-3                                                               2.5  1250                                                                              1.0                                                                              2.3 1156                                                                              145,500                                                                           3.551                                                                             151                                                                              0.860                                                                            0.718                                                                             0.140                                                                            0.013                                                                            57.1                 10 J  2.18 × 10.sup.-3                                                               2.5  1150                                                                              1.0                                                                              1.4 642 211,400                                                                           2.734                                                                             144                                                                              0.750                                                                            0.535                                                                             0.250                                                                            0.031                                                                            97.3                 __________________________________________________________________________     .sup.a Data not available.                                               

By appropriate selection of (1) Group IVB transition metal component foruse in the catalyst system; (2) the type and amount of alumoxane used;(3) the polymerization diluent type and volume; and (4) reactiontemperature, one may tailor the product polymer to the weight averagemolecular weight value desired while still maintaining the molecularweight distribution at a value below about 4.0.

The stereochemical control of the polymer formed is highly dependent onthe exact structure of the transition metal component. Those transitionmetal components containing zirconium or hafnium (M=Zr or Hf) appear tohave greater stereoregularity (fewer chain defects) than thesecontaining titanium (M=Ti). By appropriate selection of the transitionmetal component of the catalyst system a wide variety of crystallinepoly-α-olefins with differing stereochemical structure are possible.

The resins that are prepared in accordance with this invention can beused to make a variety of products including films and fibers.

The invention has been described with reference to its preferredembodiments. Those of ordinary skill in the art may, upon reading thisdisclosure, appreciate changes or modifications which do not depart fromthe scope and spirit of the invention as described above or claimedhereafter.

I claim:
 1. A process for producing crystalline poly-α-olefinscomprising the steps of(i) contacting an α-olefin monomer at atemperature and pressure sufficient to polymerize such monomer with acatalyst system comprising;(A) an alumoxane, and (B) a group IV-Btransition metal component of the formula ##STR12## wherein M is Zr, Hfor Ti in its highest formal oxidation state; R is a substituent groupwith "x" denoting the degree of substitution (x=0, 1, 2, 3 or 4) andeach R is, independently, a radical selected from a group consisting ofC₁ -C₂₀ hydrocarbyl radicals, substituted C₁ -C₂₀ hydrocarbyl radicalswherein one or more hydrogen atoms is replaced by a halogen radical, anamido radical, a phosphido radical, an alkoxy radical or any otherradical containing a Lewis acidic or basic functionality, C₁ -C₂₀hydrocarbyl-substituted metalloid radicals wherein the metalloid isselected from the Group IV A of the Periodic Table of Elements, andhalogen radicals, amido radicals, phosphido radicals, alkoxy radicals,alkylborido radicals or a radical containing Lewis acidic or basicfunctionality, or at least two adjacent R-groups are joined forming C₄-C₂₀ ring to give a saturated or unsaturated polycyclic cyclopentadienylligand; (JR'_(z-2)) is a heteroatom ligand in which J is an element witha coordination number of three from Group V A or an element with acoordination number of two from Group VI A of the Periodic Table ofElements, and each R' is, independently a radical selected from a groupconsisting of C₁ -C₂₀ hydrocarbyl radicals, substituted C₁ -C₂₀hydrocarbyl radicals where one or more hydrogen atom is replaced by ahalogen radical, an amido radical, a phosphido radical, and alkoxyradical or a radical containing a Lewis acidic or basic functionality,and "z" is the coordination number of the element J; each Q is,independently, any univalent anionic ligand or two Q's are a divalentanionic chelating ligand; T is a covalent bridging group containing aGroup IV A or V A element; L is a neutral Lewis base where "w" denotes anumber from 0 to 3; (ii) recovering a crystalline poly-α-olefin.
 2. Theprocess of claim 1, wherein the Group IV-B transition metal component isof the formula: ##STR13## wherein R¹ and R² are, independently, a C₁ toC₂₀ hydrocarbyl radicals, substituted C₁ to C₂₀ hydrocarbyl radicalswherein one or more hydrogen atom is replaced by a halogen atom; R¹ andR² may also be joined forming a C₃ to C₂₀ ring.
 3. The processes ofclaims 1 or 2 wherein J is nitrogen.
 4. The process of claim 3 wherein Ris a C₁ to C₂₀ hydrocarbyl radical, "x" is 1 and R' is a C₆ to C₂₀cyclohydrocarbyl radical or an aromatic radical.
 5. The process of claim1 wherein the Group IV-B transition metal component is of the formula:##STR14## wherein R¹ and R² are independently a C₁ to C₂₀ hydrocarbylradicals, substituted C₁ to C₂₀ hydrocarbyl radicals wherein one or morehydrogen atom is replaced by a halogen atom; R¹ and R² may also bejoined forming a C₃ to C₂₀ ring.
 6. The process of claim 5 where J isnitrogen.
 7. The process of claim 6 wherein R' is an alkyl radical orcyclic radical.
 8. The process of claim 1 wherein the Group IV-Btransition metal component is of the formula ##STR15## wherein R¹ and R²are independently a C₁ to C₂₀ hydrocarbyl radicals, substituted C₁ toC₂₀ hydrocarbyl radicals wherein one or more hydrogen atom is replacedby a halogen atom; R¹ and R² may also be joined forming a C₃ to C₂₀ring.
 9. The process of claim 8 wherein J is nitrogen.
 10. The processof claim 9 wherein R' is a cycloalkyl radical.
 11. The process of claim2, 5, or 8 wherein M is titanium.
 12. The process of claims 2 or 5wherein M is hafnium or zirconium.
 13. The process of claim 1 wherein Tis silicon, J is nitrogen and when R is an alkyl radical, R' is acyclohydrocarbyl or aromatic radical, and when "x" is 2 or 4 and the Rsubstituents form a polycyclic ring system, R' is an alkyl orcyclohydrocarbyl radical.